The steady-state absorption and fluorescence properties of (E,E,E)-1,6-diaryl-1,3,5-hexatrienes (2, aryl = 2-nitrophenyl; 3, aryl = 3-nitrophenyl; 4, aryl = 4-nitrophenyl) have been investigated in solution and in the crystalline state. The solid-state absorption spectra of 2-4 shifted to longer wavelengths than those in solution. A combination of theoretical calculations and single-crystal X-ray structure analyses shows considerable planarization of molecules in the solid state, which is mainly responsible for the spectral red shifts. The effects of intermolecular interactions on the absorption spectra appeared to be relatively small in these crystals. This is consistent with the monomeric origin of the solid-state emission. Molecule 2 was nonfluorescent in all solvents studied, probably due to the efficient nonradiative deactivation from ionic species produced by excited-state intramolecular proton transfer (ESIPT) along the C-H center dot center dot center dot O-type hydrogen bonds. The fluorescence of 3, observed only in medium polar solvents, originated from an intramolecular charge transfer (ICT*) state, while that of 4 derived from locally excited (LE*) and/or ICT* states depending on the solvent polarity. All three molecules exhibited LE* fluorescence in the solid state. No observation of ICT* emission in crystals strongly suggests the twisted geometries for ICT* (TICT) of 3 and 4 in solution. The measurable fluorescence from crystal 2 can be attributed to the restricted torsional motions in the solid excited state.